1342320 九、發明說明： 【發明所屬之技術領域】 . 本發明係關於聚合物薄片，且更具體而言係關於包含聚 、 乙烯縮丁醛之聚合物薄片，其藉由一種施於該等聚乙烯縮 丁越薄片表面之雙官能性表面改性劑而具有經增強之抗黏 連性。 【先前技術】 經塑化的聚乙烯縮丁醛（下文爲「PVB」）通常用於製造聚 . 合物溥片，該等薄片可在透光層壓板（例如安全玻璃或聚合 馨 物層壓板）中作爲夾層。安全玻璃通常指由一聚合物縮丁醛 薄片夾入兩玻璃板之間組成的透明層屋板。安全玻璃經常 用來爲建築物或汽車門窗提供透明障壁。其主要作用係吸 收（例如）由一物體撞擊産生的能量，使其不能穿透門窗，從 而最大程度地降低對室内區域的物體或人的破壞或傷害。 該薄片調配物的添加劑通常包括黏著性控制劑（「aca」） 以改良薄片對玻璃之黏著性，從而保持一適度黏著性，以 在受到衝擊時防止玻璃脫落，並且還可充分吸收能量。該 鲁 夾層薄片亦可經改良賦予安全玻璃額外的優點，例如降低 噪聲' 減少紫外線及/或紅外線之透過及/或增強門窗之美觀 性。 ' 安全玻璃通常藉由下述方法形成：將兩層玻璃及—塑性 夾層（例如PVB)組裝成一預壓結構’形成—預製層壓板再 拋光成一光亮的層壓板。該組裝階段包括平放一塊破璃， · 於其上覆蓋-PVB薄片，放置第二塊玻璃，，然後根據玻㉟ 、 93796.doc 1342320 層邊緣去除多餘的PVB薄片。 塑性夾層通常藉由下述來製造：將PVB聚合物與一或多 種増塑劑混合，且視情況可與—或多種其他成份混合，然 後再將該混合物熔化處理成薄片&，通常要將其收集起來 並捲起來以方便儲存及運輸。在汽車擋風玻璃的層壓製程 中，通常自PVB卷上切割下若干塊PVB薄片，並將該等薄片 修整爲適當形狀及/或堆疊以便於組裝。然後，自該堆疊取 下塊經切割之薄片並使用一剛性基板（例如，具有特定光 予口《質之玻璃板）以分層佈置方式進行組裝，從而使該剛性 基板之一表面與該切割片之一表面緊密接觸以形成一預壓 層壓板組件。或者，該層壓板組件可藉由將多層切割片與 多層剛性板交替插置而形成。 無論是成卷形式的還是堆疊形式的塑化PVB薄片，在環 境溫度下皆具有自黏附（「黏連」）趨勢，通常在層壓製程之 則或期間會遇到此情況。爲了增強pVB的抗黏連性，人們 做了 °午夕嘗5式’包括對薄片表面之機械粗糖化處理（例如壓 、’文）在薄片表面上施用一粉末（例如碳酸氫納）及對pvB薄 片表面進行化學或物理處理。遺憾的是，該等表面處理經 系會引起非期望之作業或玻璃黏著性問題。在避免上述黏 連之另一常用作業中，PVB薄片可與另一薄片材料例如聚 乙烤父替插置’或在冷藏溫度（例如，自約5至約15 °C )下儲 存及運輸。然而，對於標準PVB薄片之多種改變，例如爲 增強降°喿功能而納入高含量增塑劑的PVB薄片，即使在冷 藏條件下亦可發生黏連。 93796.doc 1342320 另外，有人建議於PVB中納入多種抗黏連材料。然而， PVB中納入該等材料會對製得層壓板之光學特性或ρνΒ薄 片對玻璃之黏著性産生不利影響。 因此，需要經進一步改良之方法來增強ρνβ薄片之抗黏 連性，且不會對層壓板之光學透明度及所得ρνΒ薄片對玻 璃之黏著性產生不利影響。 【發明内容】 現已驚奇地發現，根據本發明，將一雙官能性表面改性 劑施於一聚合物薄片表面可增強該聚合物薄片之抗黏連特 性且不會産生不利的光學及黏著性效應。亦已發現，藉由 一種製造方法可使聚合物薄片表面獲得抗黏連特性，該方 法包括將一雙官能性表面改性劑施於該聚合物薄片表面。 另外，本發明包括經層壓之安全玻璃，其包括兩片玻璃及 塊位於一者之間的聚合物薄片失層，其中該聚合物薄片 含有一雙官能性表面改性劑，該改性劑施於該薄片之表面。 本文揭示了表面施有雙官能性表面改性劑的聚合物薄 片、製造其表面含有雙官能性表面改性劑的聚合物薄片之 方法及增強聚合物薄片抗黏連性之方法的實例性實施例。 在一貫施例中’聚合物4片包含聚乙稀縮丁链、—納入該 聚乙烯縮丁醛的增塑劑及一施於經塑化聚乙烯縮丁搭表面 的雙官能性表面改性劑。該雙官能性表面改性劑包括一抗 黏連片段及一相容片段。該抗黏連片段包括一烴基，例如 一直鏈烴基。該相容片段包括一極性基團例如一續酸基、 硫酸基、羧基或磷酸基。因此，該抗黏連片段及相容片段 93796.doc 1342320 可將對聚合物薄片的抗黏連性及相容性之雙官能性分別賦 予该試劑。 · 本發明之一種製造一聚合物薄片之方法包括將一聚合物 熔化處理成一薄片以及將一雙官能性表面改性劑施於該聚 合物薄片表面，該雙官能性表面改性劑包括一抗黏連片段 及一相谷片段。該抗黏連片段包括一烴基，例如一直鏈烴 基。該相容片段包括一極性基團，例如一磺酸基、硫酸基、 敌基或碟酸基。 ’ 本發明之層壓安全玻璃包括兩片玻璃及一位於二者之間 # 的-聚合物薄片央層，其t該聚合物薄片含有一施於其表 面的雙官能性表面改性劑’該雙宫能性表面改性劑包括一 抗黏連片段及一相容片段。 【實施方式】 根據本發明，-薄片形式的塑化聚合物含有一施於該聚 合物薄片表面的雙官能性表面改性劑。應瞭解，盡管下述 實施例中之聚合物皆爲PVB，但該聚合物可爲任何具有一 適宜玻璃㈣溫度㈣合物。典型的該等聚合物包括聚乙 烯縮丁搭、聚胺基甲酸酿1氣乙稀、聚(乙稀共聚·醋酸 乙烯酯）、上述之組合及諸如卜# 連如此類。該雙官能性表面改性劑 可增強該聚合物薄片之抗黏連性且包括—抗黏連片段及一 相容片段。該抗點連片段包括一烴基，例如一直鏈烴基。 s玄相容片段包括一極性基團，办丨， 錢例如-磺酸基、硫酸基、羧 基或磷酸基’可賦予該聚合物薄片適宜的相容性。1342320 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to polymer sheets, and more particularly to polymer sheets comprising poly(vinyl butyral), which are applied by such a polymerization The vinylidene has a bifunctional surface modifier on the surface of the sheet to have enhanced blocking resistance. [Prior Art] Plasticized polyvinyl butyral (hereinafter "PVB") is commonly used in the manufacture of polymeric crepe sheets which are available in light transmissive laminates (eg, safety glass or polymeric melamine laminates). ) as a mezzanine. Safety glass generally refers to a transparent laminate formed by sandwiching a polymer of butyral sheets between two glass sheets. Safety glass is often used to provide transparent barriers to buildings or car windows and doors. Its primary function is to absorb, for example, the energy generated by the impact of an object so that it does not penetrate the doors and windows, thereby minimizing damage or injury to objects or people in the indoor area. The additive to the flake formulation typically includes an adhesion control agent ("aca") to improve the adhesion of the flake to the glass, thereby maintaining a moderate degree of adhesion to prevent the glass from falling off during impact and also to fully absorb energy. The Lu sandwich sheet can also be modified to give the safety glass additional advantages such as reduced noise 'reducing the transmission of ultraviolet and/or infrared light and/or enhancing the aesthetics of the door and window. 'Safety glass is usually formed by assembling two layers of glass and a plastic interlayer (e.g., PVB) into a pre-compressed structure'-preformed laminate and then polished into a bright laminate. The assembly stage consists of laying a piece of glass flat on top of it, covering it with a PVB sheet, placing a second piece of glass, and then removing excess PVB sheets from the edges of the glass 35, 93796.doc 1342320 layer. Plastic interlayers are typically made by mixing a PVB polymer with one or more plasticizers, and optionally with or with a plurality of other ingredients, and then melting the mixture into flakes & It is collected and rolled up for storage and transportation. In the lamination of automotive windshields, several PVB sheets are typically cut from a PVB roll and trimmed into suitable shapes and/or stacks for assembly. Then, the cut piece is removed from the stack and assembled in a layered arrangement using a rigid substrate (for example, a glass plate having a specific light port) so that one surface of the rigid substrate and the cut One of the sheets is in intimate contact to form a pre-compressed laminate assembly. Alternatively, the laminate assembly can be formed by alternately inserting a plurality of dicing sheets with a plurality of rigid sheets. Plasticized PVB sheets, whether in roll form or in stacked form, have a tendency to self-adhere ("stick") at ambient temperatures, which is typically encountered during or during the lamination process. In order to enhance the anti-blocking property of pVB, it has been done to include a powder (for example, sodium bicarbonate) on the surface of the sheet and a mechanical coarse saccharification treatment (for example, pressing, 'text) on the surface of the sheet. The surface of the pvB sheet is chemically or physically treated. Unfortunately, such surface treatment processes can cause undesired work or glass adhesion problems. In another common practice to avoid such adhesion, the PVB sheet can be stored and transported with another sheet material, such as a polyethylene bake, or at a refrigerated temperature (e.g., from about 5 to about 15 °C). However, for various changes to standard PVB flakes, such as PVB flakes incorporating a high level of plasticizer to enhance the 喿 喿 function, adhesion can occur even under cold storage conditions. 93796.doc 1342320 In addition, it has been suggested to include multiple anti-adhesion materials in PVB. However, the incorporation of such materials into the PVB can adversely affect the optical properties of the resulting laminate or the adhesion of the ρνΒ film to the glass. Therefore, a further improvement is required to enhance the anti-blocking property of the ρνβ sheet without adversely affecting the optical transparency of the laminate and the adhesion of the resulting ρνΒ sheet to the glass. SUMMARY OF THE INVENTION It has now surprisingly been found that the application of a bifunctional surface modifier to the surface of a polymer sheet enhances the anti-blocking properties of the polymer sheet without adverse optical and adhesion, in accordance with the present invention. Sexual effects. It has also been discovered that the surface of the polymer sheet can be rendered anti-blocking by a manufacturing process which involves applying a bifunctional surface modifier to the surface of the polymer sheet. Additionally, the present invention comprises a laminated safety glass comprising two sheets of glass and a polymer sheet having a block between one layer, wherein the polymer sheet contains a bifunctional surface modifier, the modifier Apply to the surface of the sheet. Disclosed herein are exemplary embodiments of a polymer sheet having a bifunctional surface modifier applied thereto, a method of producing a polymer sheet having a bifunctional surface modifier thereon, and a method of enhancing the blocking resistance of the polymer sheet. example. In a consistent example, 'polymer 4 sheets contain polyethylene condensed chains, plasticizers incorporating the polyvinyl butyral, and a bifunctional surface modification applied to the surface of the plasticized polyethylene Agent. The bifunctional surface modifier comprises an anti-adhesion fragment and a compatible fragment. The anti-adhesion fragment comprises a hydrocarbon group such as a straight chain hydrocarbon group. The compatible fragment includes a polar group such as a carboxylic acid group, a sulfate group, a carboxyl group or a phosphate group. Therefore, the anti-adhesion fragment and the compatible fragment 93796.doc 1342320 can be imparted to the reagent by the bifunctionality of the blocking resistance and compatibility of the polymer sheet, respectively. A method of making a polymer sheet of the present invention comprising: melting a polymer into a sheet and applying a bifunctional surface modifier to the surface of the polymer sheet, the bifunctional surface modifier comprising a primary antibody Adhesive fragments and one phase valley fragments. The anti-adhesion fragment comprises a hydrocarbon group such as a straight chain hydrocarbon group. The compatible fragment includes a polar group such as a monosulfonate, a sulfate group, an ester group or a disc acid group. The laminated safety glass of the present invention comprises two sheets of glass and a central layer of a polymer sheet between the two, wherein the polymer sheet contains a bifunctional surface modifier applied to its surface. The dual-energy surface modifier includes an anti-adhesion fragment and a compatible fragment. [Embodiment] According to the present invention, a plasticized polymer in the form of a sheet contains a bifunctional surface modifier applied to the surface of the polymer sheet. It should be understood that although the polymers in the following examples are all PVB, the polymer may be any suitable glass (iv) temperature (tetra) compound. Typical of such polymers include polyethylene condensed butadiene, polyaminocarbamic acid, ethylene oxide, poly(ethylene copolymer, vinyl acetate), combinations of the foregoing, and the like. The bifunctional surface modifier enhances the blocking resistance of the polymer sheet and includes an anti-blocking fragment and a compatible fragment. The anti-pointing fragment comprises a hydrocarbon group such as a straight chain hydrocarbon group. The s-compatible fragment includes a polar group, and the money such as a -sulfonate group, a sulfate group, a carboxyl group or a phosphate group can impart suitable compatibility to the polymer sheet.
觸常藉由已知縮酸化方法來製備，該等方法包括在 93796.doc 1342320 酸觸媒之存在下使PVOH與丁醛反應，隨後中和該觸媒、分 離、穩定並乾燥樹脂。該聚合物通常包含約13至約3〇重量 A(Wt_ /◦)的沒基（按PVOH計），較佳包含約1 5至約22 Wt %羥 基（按P VOH計）。該聚合物進一步包含至多約〗〇糾％殘餘酯 基，較佳包含至多約3〜,％殘餘酯基（以聚乙酸乙烯酯計）， 其餘爲一縮醛，較佳爲丁縮醛，但視情況可包含其他縮醛 基團，例如，2-乙基己烷基。通常，PVB產品具有一超過約 70,000克/莫耳（g/m〇le)i分子量。本文所用術語「分子量」 應解釋爲平均分子量。製備pvB之適宜方法的細節已爲熟 諳此項技術者所熟知。PVB可自S〇lutia公司（St L〇uis， Missouri)以ButvarTM樹脂之商品名購得。 於PVB聚合物中可添加多種添加劑，以增強其在一終產 品中之性能。該等添加劑包括（但不限於）染劑、色素、穩定 劑（例如，紫外線穩定劑）、抗氧化劑、上述添加劑之組合及 諸如此類。 PVB薄片中通常包含約2〇至8()且更常見爲25至6〇份增塑 劑/100份樹脂（「phr」）。增塑劑之量會影響pvB薄片的％。 通币增加增塑劑之置會降低Tg。一般情況下，pvB薄片之 Tg爲約3CTC或以下。Tg低於約2〇。(：之1)¥6薄片經常用作聲 學PVB薄片。常用的增塑劑爲多㈣或多元醇的醋。適合 的增塑劑包括（例如）三乙二醇二_(丁酸2_乙基酯）、三乙二醇 一-(己酸2-乙基酯）、三乙二醇二庚酸酯、四乙二醇二庚酸 、己二酸二己基醋、己二酸二辛基酿、己二酸己基酿環 己基酯、己二酸庚基酯與己二酸壬基酯的混合物、己二酸 93796.doc 1342320 一異壬基酯、己二酸庚基酯壬基酯、癸二酸二丁基酯、聚 合物增塑劑（例如油改性癸二酸醇酸縮合物）及磷酸酯與己 二酸酯的混合物（例如揭示於美國專利第3,841，89〇號中者） 及己二酸酯（例如揭示於美國專利第4,丨44,2丨7號中者）。亦 不使用由C4至C9烧醇及C4至ci0環烧醇制得的己二酸酯混 合物作爲增塑劑，如揭示於美國專利第5,013,779號中者。 較佳增塑劑爲C6至C8己二酸酯，例如己二酸二己基酯。 PVB聚合物及增塑劑添加劑可經熱處理構形爲薄片形 式。一種形成PVB薄片之實例性方法包括藉由使熔融態pvB 樹脂+增塑劑+添加劑（下文稱「熔體」）通過一薄片壓模（例 如一具有開口的壓模，該開口沿一方向之尺寸顯著大於沿 垂直方向之尺寸）而擠出該熔體。形成pVB薄片之另一實例 性方法包括將熔融態樹脂或半熔融態樹脂自一壓模澆注至 一輥子上，固化該樹脂並隨後移去該固化樹脂薄片。在任 實鈿例中，薄片任一面或兩面的表面紋理皆可藉由調整 壓模開口表面或在輥子表面設置紋理來控制。控制薄片紋 理的其他技術包括改變反應材料的參數’例如樹脂及/或增 塑劑的含水量、熔化溫度或上述參數之組合。另外，可將 薄片構形爲具有若干間隔凸起來界定暫時的表面不規則 性，以便在層壓製程中實施脫氣處理，隨後，該層壓製程 之高溫及高壓可使該等凸起熔化於薄片，由此獲得光滑的 表面。在任—實施例中，擠出成型的薄片之厚度爲約0.3至 約2.5毫米（mm)。 雙官能性表面改性劑較佳作爲—塗層施於p v B薄片之表 93796.doc •10- 1342320 面且包括一抗黏連片段及一相容片段。改性劑之實例性實 化例包括霞基苯磺酸酯（RC6H4S〇3M)、烷基磺酸鲳 (RS03M)、燒基硫酸酷（R〇s〇3M)、烷基羧酸酷（Rc〇〇m)、 *院氧幾基脂（R(〇CH2CH2)n〇cH2C〇〇M；)及烷基磷酸酯 (ROP〇3M2)，其中μ爲氫或一金屬陽離子（例如納、鉀、鎮、 鈣及諸如此類）或一銨離子，R爲一烷基且η(重復單元的數 I )大於1。較佳地，該試劑至少包括一磺酸基。在一較佳 實例性實施例巾，如下所示，抗黏連片段爲X且相容片段爲 具有一帶正電荷的抗衡離子Υ的磺酸基（-S03-Y)。最終結 構呈下述形式： 、17The abatement is prepared by a known acidification process which comprises reacting PVOH with butyraldehyde in the presence of a 93796.doc 1342320 acid catalyst, followed by neutralization of the catalyst, separation, stabilization and drying of the resin. The polymer typically comprises from about 13 to about 3 Å by weight of A (Wt Å / ◦) of ruthenium (based on PVOH), preferably from about 15 to about 22 TW % of hydroxyl groups (based on P VOH). The polymer further comprises up to about 5% by weight of residual ester groups, preferably containing up to about 3% by weight of residual ester groups (based on polyvinyl acetate), the balance being an acetal, preferably butyral, but Other acetal groups may be included as appropriate, for example, 2-ethylhexyl. Typically, PVB products have a molecular weight in excess of about 70,000 grams per gram (g/m〇le). The term "molecular weight" as used herein shall be interpreted as the average molecular weight. Details of suitable methods for preparing pvB are well known to those skilled in the art. PVB is commercially available from S〇lutia, Inc. (St L〇uis, Missouri) under the trade name ButvarTM resin. A variety of additives can be added to the PVB polymer to enhance its performance in a final product. Such additives include, but are not limited to, dyes, pigments, stabilizers (e.g., UV stabilizers), antioxidants, combinations of the foregoing, and the like. The PVB flakes typically comprise from about 2 to 8 (and more typically from 25 to 6 parts plasticizer per 100 parts resin ("phr"). The amount of plasticizer affects the % of pvB flakes. Increasing the amount of plasticizer in the currency will lower the Tg. In general, the Tg of the pvB flakes is about 3 CTC or less. The Tg is less than about 2 〇. (1) The ¥6 sheet is often used as an acoustic PVB sheet. Commonly used plasticizers are vinegars of poly(tetra) or polyhydric alcohols. Suitable plasticizers include, for example, triethylene glycol di-(2-ethyl butyrate), triethylene glycol mono-(2-ethyl hexanoate), triethylene glycol diheptanoate, Tetraethylene glycol diheptanoic acid, dihexyl adipate vinegar, dioctyl adipate, adipic hexyl dicyclohexyl adipate, a mixture of heptyl adipate and decyl adipate, Acid 93796.doc 1342320 1-isodecyl ester, heptyl adipate decyl ester, dibutyl sebacate, polymeric plasticizer (eg oil modified sebacic acid condensate) and phosphate Mixtures with adipates (e.g., as disclosed in U.S. Patent No. 3,841,89) and adipates (e.g., as disclosed in U.S. Patent No. 4, No. 4, No. 4, No. 7). A mixture of adipic acid esters prepared from C4 to C9 ani alcohol and C4 to ci0 cycloalcohol is also not used as a plasticizer, as disclosed in U.S. Patent No. 5,013,779. Preferred plasticizers are C6 to C8 adipates, such as dihexyl adipate. The PVB polymer and plasticizer additive can be heat treated to form a sheet. An exemplary method of forming a PVB sheet includes passing a molten state pvB resin + plasticizer + additive (hereinafter referred to as "melt") through a sheet die (for example, a stamper having an opening in one direction) The melt is extruded by exposing the melt to a size that is significantly larger than the dimension in the vertical direction. Another exemplary method of forming a pVB sheet includes casting a molten resin or a semi-molten resin from a stamper onto a roll, curing the resin and then removing the cured resin sheet. In any of the examples, the surface texture of either or both sides of the sheet can be controlled by adjusting the surface of the stamper opening or setting the texture on the surface of the roll. Other techniques for controlling the texture of the flakes include altering the parameters of the reactive material, such as the water content of the resin and/or plasticizer, the melting temperature, or a combination of the above parameters. In addition, the sheet may be configured to have a plurality of spaced projections to define temporary surface irregularities for performing a degassing process during the lamination process, and then the high temperature and high pressure of the lamination process may cause the protrusions to melt A thin sheet, thereby obtaining a smooth surface. In any of the embodiments, the extruded sheet has a thickness of from about 0.3 to about 2.5 millimeters (mm). The bifunctional surface modifier is preferably applied as a coating to the pvB sheet of Table 93796.doc • 10-1342320 and includes an anti-adhesion fragment and a compatible fragment. Illustrative examples of modifiers include oxime benzenesulfonate (RC6H4S〇3M), sulfonium alkylsulfonate (RS03M), sulphuric acid sulphate (R〇s〇3M), and alkyl carboxylic acid (Rc) 〇〇m), *House oxygen base grease (R(〇CH2CH2)n〇cH2C〇〇M;) and alkyl phosphate (ROP〇3M2), where μ is hydrogen or a metal cation (eg, sodium, potassium, Town, calcium and the like or a monoammonium ion, R is monoalkyl and η (number I of repeating units) is greater than one. Preferably, the reagent comprises at least a sulfonic acid group. In a preferred exemplary embodiment, as shown below, the anti-adhesion fragment is X and the compatible fragment is a sulfonic acid group (-S03-Y) having a positively charged counterion oxime. The final structure is in the form: , 17
族基團及芳香族基團之組合（例如一直; (例如笨基），或其一組合），其含有至少 含有約8至50個碳原子。較佳地，抗黏七 芳香族化合物，其較佳具有一可賦予男 連特性的分子結構，其形式爲： 爲氣、一銨離子或一鹼性金屬離子。具 脂肪族基團、一芳香族基團或一脂肪 Ϊ之組合（例如一直鏈烴基，一環狀基團 組合），其含有至少約δ個碳原子且更佳 子。較佳地，抗黏連片段X爲—脂肪族_ 具有一可賦予聚合物薄片適宜抗黏 其中R爲一包含約2至 另一方面，改性劑之 間具有充足的相容力，A combination of a group of groups and an aromatic group (e.g., always; (e.g., stupid), or a combination thereof) containing at least about 8 to 50 carbon atoms. Preferably, the anti-adhesive aromatic compound preferably has a molecular structure which imparts a male character in the form of: a gas, an ammonium ion or an alkali metal ion. A combination of an aliphatic group, an aromatic group or a fatty hydrazone (e.g., a straight chain hydrocarbon group, a cyclic group combination) containing at least about δ carbon atoms and more preferably. Preferably, the anti-adhesion fragment X is - aliphatic - having a suitable anti-adhesive property to the polymer sheet, wherein R is from about 2 to the other, and the modifier has sufficient compatibility.
包含約2至約44個碳原子的直鏈烴基。 改性劑之相容片段（例如 ’改^劑之相容片段（例如-S〇3Y)^VB薄片之 的相容力，從而使該改性劑與PVB薄片之 之間具 93796.doc 320 320 有一定的相容性 以避免或至少最大程度地降低對PVB薄 片之光學特性的不利影響’同時有效地增強PVB薄片的抗 黏連性。具體而言，適宜極性基團對PVB薄片的充分相容 力可使改性劑在PVB表面形成均勻的薄塗層，從而將透過 PVB的光散射程度降至最低。 用作雙官能性表面改性劑之較佳化合物爲脂肪族·芳香 族磺酸化合物。尤佳者爲十二烷基苯磺酸（下文稱爲 「DSH」），其式爲： so3h CH3(CH2)„ DSNa」或 及十一炫基笨續酸之鈉或鎖鹽（下文稱爲 「DSMg」）’其一實例性實施例具有下式： CH3(CH2),A linear hydrocarbon group containing from about 2 to about 44 carbon atoms. A compatible fragment of the modifier (eg, a compatible fragment of the modified agent (eg, -S〇3Y)^VB sheet, such that the modifier and the PVB sheet are between 93796.doc 320 320 has a certain compatibility to avoid or at least minimize the adverse effect on the optical properties of the PVB flakes' while effectively enhancing the anti-blocking properties of the PVB flakes. Specifically, suitable polar groups are sufficient for PVB flakes. The compatibility allows the modifier to form a uniform thin coating on the surface of the PVB, thereby minimizing the degree of light scattering through the PVB. The preferred compound for use as a bifunctional surface modifier is an aliphatic aromatic sulphide. An acid compound, especially a dodecylbenzenesulfonic acid (hereinafter referred to as "DSH"), which is: so3h CH3(CH2)„DSNa” or a sodium or a lock salt of eleven Hereinafter, it is referred to as "DSMg"). An exemplary embodiment thereof has the following formula: CH3(CH2),
— S03Na(或 Mg) 且其可與DSH結合使用。 將雙官能性表面改性劑施於PVB薄片上之實例性技術包 括（但不限於）以物理方法將試劑施於薄片表面。試劑之物理 施予方法包括（但不限於）喷塗技術、浸潰技術、凹板塗佈技 術及諸如此類。在一實例性喷塗技術中’將試劑置於（例如 分散或溶解於）一液體載劑中，經霧化後至少將其喷灑至 PVB薄片-側表面之段。該㈣可爲水性溶液或溶於 溶劑(例如乙醇、甲醇、兩酮、甲基乙基酮、上述之組合及 諸如此類）之溶液。將載劑塗施於pvB薄片後，該載劑將會 揮發掉，因此只留下改性劑附著於PVB薄片表面。載劑中 93796.doc 1342320 之改性劑濃度應足以使薄片表面達成期望的試劑濃度。在 一典型的噴塗技術中，載劑中雙官能性表面改性劑之濃度 以液體總重量計爲約0.1至約40 wt.0/〇。 在一浸潰技術之實例性實施例中，係將PVB薄片浸沒於 栽有改性劑之水性溶液或溶於溶劑之溶液中，當取出薄 片並使載劑揮發掉之後，該薄片表面即敷有該改性劑。在 浸漬技術中，載劑中之改性劑濃度較佳爲約〇 〇1至約2〇 0更佳爲約〇. 〇 5至約5 w t. % ’且更佳爲約〇. 1至約2 wt.0/〇 〇 在一凹板塗佈技術之實例性實施例令，係將雙官能性表 面改性劑置於（例如分散或溶解於）一液體載劑中，並用一凹 板塗佈裝置將液體載劑轉移至聚合物薄片上。隨後可藉由 例如蒸發自聚合物薄片表面去除該載劑。 所得的表面上具有雙官能性表面改性劑之pvB薄片之黏 連值至少比不含雙官能性表面改性劑之pvB樹脂聚合物薄 片之黏連值低约50%，較佳至少低約7〇%，且更佳至少低約 9〇 /。。表面施有雙官能性表面改性劑之pVB薄片之透明度可 藉由1測霧度值來確定，該霧度值爲一因散射而使其方向 偏離入射光束方向超過一特定角度之光線的透過百分比， 可按照ASTMD1003來確定。較佳地，該霧度值低於約3%， 更佳低於約2% ’且最佳低於約。 雙官能性表面改性劑之存在對表面含有雙官能性表面改 ，劑的卿薄片之黏著性基本上沒有影響。較佳地，該點 著性值（PVB薄片點附於玻璃之程度的量化值）與一表面未 93796.doc 1342320 施有雙宫能性表面改性劑的PVB薄片之黏著性值間的差值 在約20%以内，更佳在約1〇%以内，且最佳在約5%以内。 黏著性可藉由（例如）一擊打黏著性測試量測，該測試可量測 PVB薄片及破璃之間的結合力。 實例 在該等實例中使用以下測試： 1.擊打黏著性測試 在標準壓熱層壓條件下製備雙層玻璃層壓板樣品。將該 等層壓板冷卻至-1 7.8 t並用一錘子以人工擊打至玻璃破 碎。然後去除所有未黏附至PVB薄片上的碎玻璃，並對剩 下的黏附於該PVB薄片之玻璃量與一組標準實施目測比 車乂 °玄荨仏準對應於一刻度標尺，表示點附於pvb薄片上 的玻璃的不同數量。具體而言，擊打標準爲零表示沒有剩 餘的玻璃黏附於PVB薄片上。擊打標準爲1〇表示1〇〇%的玻 璃保持黏附於PVB薄片上。 2. 黏連測試 該測試係量測PVB薄片的自身黏連傾向。在此測試中， 切割下兩矩形膜片並完全重疊地成對放置在一起。使每一 對的上層薄片黏著於一塊相應大小的條帶上。將成對膜片 置於兩鋼板中心，並在7。(：之溫度下對該組件施加仍让以壓 力持續24小時。在90度剝離測試中用剝離測試裝置以每分 鐘84英吋的速度剝離該等條帶。黏連力以每線吋磅數（pLi) 來表示。 3. %霧度（透明度）測試 93796.doc •14- 1342320 該測試用於量測由PVB薄片製成的層壓板之透明度，其 係依照ASTM D1003-6 1(1 977年再次審定，A程序）實施，採 用C光源’觀察角度爲2度，量測霧度值之裝置使用自 Hunterlab購得的D25型霧度計。 實例1 : PVB薄片之製造 使用一高強度混合器預先混合用以製造PVB薄片的塑化 PVB調配物，該調配物包含1〇〇重量份數的pvB樹脂（羥基含 里以PVOH計爲16.3 wt·%)、52份三乙二醇二(己酸2-乙基酯） 及其他添加劑（包括黏著性控制劑、紫外線吸收劑、抗氧化 劑及其他成份）。於一擠出機内熔化該塑化調配物並使其以 熔體形式通過一薄片壓模（該壓模前端具有一矩形模口，藉 由一對相對的唇邊界定）。該熔體的溫度約爲i 8〇<t。擠出 薄片之厚度約爲3〇密耳（0 76毫米）。薄片每一側皆具有—粗 I表面可在層壓製程期間自薄片與玻璃間的介面去除空 氣。 、二 實例2 : P VB薄片之浸漬塗佈 將未加工 改性劑之 在浸漬塗 溫下實施 對照樣品 能性表面 及諸如此 霧度測試 PVB 4片之浸潰塗佈藉由下述實施：在室溫下 的PVB 4片分別浸人其中含有相應雙官能性表面 水溶液-段時Pb卜例如，2〇秒鐘，然後乾燥之。 =將—些樣品浸人-淡水池中。—些樣品在高 塗佈《在—調内將經浸潰塗佈之樣品及 之濕度調節爲〇.35%。浸潰條件之實例，包括雙官 改性劑之類型（表面改性劑）、溶液濃度、浸潰時間 類、連同1轉浸潰樣品之擊打測試、黏連測試及 93796.doc 1342320 之結果皆分別列示於表1 _4甲。 用聚苯乙烯磺酸鈉鹽（pSSNa)、DSH或DSNa的水性溶液 次潰塗伟樣品並隨後於水中實施一與記錄的浸潰時間相等 的第二次浸漬’然後實施擊打測試、黏連測試及霧度測試， 測試結果如下表1所示： 表1 樣品號 表面 改性劑 對照 >農度 浸潰時間黏連值 (wt·%) (秒） (PLI) ~ - 2.00 霧度％ 0.50 擊打黏著 性測試 6.6 2. 3. 4. 5. 對照 PSSNa3 2.0 60l DSH 2.0 601 DSNa 2.0 601 DSH 2.0 60' DSH 2.0 40' DSH 2.0 20' DSH 2.0 201，: DSH 1.0 20丨 DSH 0.5 201 1.86 0.06 0.75 2.96 6.6 6.5 3.2 6.8 4.8 6.5 9.0 9.0 9.0 7.3 0.45 0.40 0.50 0.40 0.30 0.30 0.30 0.30 0.30 0.30 其持續時間與記錄的浸潰時 將溶液溫度升至40。(：。 3PSSNa代表聚苯乙烯磺酸之鈉鹽。 在室溫下以不同的浸潰時間^種濃度的DSH水性溶液 浸潰塗佈樣品後，對其實施擊打測試、黏連測試及霧度測 試’測試結果如下表2所示： 93796.doc -16- 1342320 表2 樣品號 表面 改性劑 濃度 (wt. %) 浸潰時間 (秒） 黏連值 (PLI) 霧度％ 擊打黏著 性測試 12. - - - 4.14 0.40 7.5 對照 13. DSH 2.0 60 0.10 0.30 9.0 14. DSH 2.0 20 0.12 0.40 9.0 15. DSH 1.0 60 0.15 0.40 9.0 16. DSH 1.0 20 0.24 0.40 9.0 17. DSH 0.5 60 0.40 0.30 9.0 18. DSH 0.5 20 0.51 0.40 8.8 在室溫下以不同的浸潰時間用1 wt.% DSH/DSNa混合物 (其具有多種不同的DSH/DSNa重量比）之水性溶液浸潰塗 佈樣品後，對其實施擊打測試、黏連測試及霧度測試，測 試結果如下表3所示： 表3 樣品號 表面改性劑 濃度 浸潰時間 黏連值 霧度％ 擊打黏著 (wt. %) (秒） (PLI) 性測試 19. - - - 2.80 0.50 6.2 對照 20. 100% DSH/ 0% DSNa 1.0 60 0.03 0.40 9 21. 100% DSH/ 0% DSNa 1.0 20 0.04 0.40 9 22. 75% DSH/ 25% DSNa 1.0 60 0.04 0.40 9 23. 75% DSH/ 25% DSNa 1.0 20 0.07 0.60 9 24. 50% DSH/ 50% DSNa 1.0 60 0.05 0.40 4.5 25. 50% DSH/ 50% DSNa 1.0 20 0.06 0.50 6.5 在室溫下用1 wt.°/〇的DSH/DSNa(或DSMg)混合物（其具有 多種不同的DSH/DSNa(或DSMg)重量比）之水性溶液浸潰塗 93796.doc 1342320 佈樣品20秒鐘後，對其實施擊打測試、黏連測試及霧度測 試，測試結果如下表4所示： 表4 樣品號 表面改性劑 濃度 (wt.%) 浸潰時間 (秒） 黏連值 (PLI) 霧度％ 擊打黏著 性測試 26. - - 3.50 0.6 6 對照 27. 100% DSH/ 0% DSNa 1 20 0.05 0.5 9 28. 75% DSH/ 25% DSNa 1 20 0.05 0.5 9 29. 50% DSH/ 50% DSNa 1 20 0.08 0.5 7.8 30. 25% DSH/ 75% DSNa 1 20 0.07 0.5 3 31. 5% DSH/ 95% DSNa 1 20 0.08 0.5 0 32. 0%DSH/ 100% DSNa 1 20 0.09 0.5 0 33. 75% DSH/ 25% DSMg 1 20 0.07 0.5 9 34. 50% DSH / 50% DSMg 1 20 0.05 0.5 9 35. 25% DSH/ 75% DSMg 1 20 0.10 0.5 8 36. 5% DSH / 95% DSMg 1 20 0.28 0.5 0 37. 0% DSH/ 100% DSMg 1 20 0.23 0.5 0 38. - - - 2.06 0.4 6.5 對照 39. 20% DSH/ 80% DSMg 1 20 0.02 0.3 1.5 40. 40% DSH/ 60% DSNa 1 20 0.04 0.4 8 41. 30%D SH/ 70% DSNa 1 20 0.04 0.3 7.5 93796.doc · 18· 1342320 42. 43. 20% DSH/ 80% DSNa 10% DSH/ 90% DSNa 20 20 0.07 0.22 0.3 0.3 6.5 5.5 上述表面施有雙官能性表面改性劑之”β薄片實施例通 常適於作爲層厂堅安全玻璃之PVB夹層。另夕卜因爲該等薄 片表面之改良，上述實施例尤1 4八m U尤其適合用於製造非交替插置 式聲學PVB夾層産品。 與表面未施有雙官能性表面改性劑之削薄片相比，上 述PVB薄片還具有若干其他優點。首先，表面施有雙官能 性表面改性劑之PVB薄片的#連超勢顯著降低，同時在將 薄片納入層壓安全玻璃中時可保持充分的光學品質及其對 玻璃的適當黏著性。黏連趨勢的降低使得該pvB薄片可在 較低的冷藏或交替插置的要求下儲存或運輸。其次，因爲 上文揭示之雙官能性表面改性劑至少片段與該Μ相容， 故，無需再實施額外的處理步驟，例如清洗薄片以去除粉 末。彼等熟諸此項技術者可很容易地明瞭本發明之其他優點。 僅管已參考㈣性實施例_了本發明，但彼等孰諸此 項技術者應瞭解’㈣等實施例可作多種改變且可用其等 價項替代其中之要素而不背離本發明之範圍。另外，爲適 應一具體情況或材料亦可對本發明之教示實施多項改良且 不背離本發明之基本範圍。因此，本文並非意欲將本㈣ 限制於所揭示的作爲實施本發明最佳設想模式之特定實施 例:而是意欲使本發明涵蓋所有屬於隨附中請專利: 範脅内的實施例。 93796.doc -19-– S03Na (or Mg) and it can be used in combination with DSH. Exemplary techniques for applying a bifunctional surface modifier to a PVB sheet include, but are not limited to, physically applying the agent to the surface of the sheet. Physical application methods for reagents include, but are not limited to, spray coating techniques, impregnation techniques, gravure coating techniques, and the like. In an exemplary spray technique, the reagent is placed (e.g., dispersed or dissolved) in a liquid carrier and, after atomization, at least sprayed onto the PVB sheet-side surface section. The (d) may be an aqueous solution or a solution dissolved in a solvent such as ethanol, methanol, ketone, methyl ethyl ketone, a combination of the above, and the like. After the carrier is applied to the pvB flakes, the carrier will evaporate, leaving only the modifier attached to the surface of the PVB flakes. The concentration of the modifier in the carrier 93796.doc 1342320 should be sufficient to achieve the desired reagent concentration on the surface of the sheet. In a typical spray technique, the concentration of the bifunctional surface modifier in the carrier is from about 0.1 to about 40 wt.0 / Torr based on the total weight of the liquid. In an exemplary embodiment of an impregnation technique, the PVB flakes are immersed in a solution in which the modifier is applied or dissolved in a solvent, and when the flakes are removed and the carrier is volatilized, the surface of the flakes is applied. There is this modifier. In the impregnation technique, the concentration of the modifier in the carrier is preferably from about 至1 to about 2 〇0, more preferably from about 〇. 5 to about 5 w t. % 'and more preferably about 〇. An exemplary embodiment of about 2 wt.0 / 〇〇 in a gravure coating technique is to place (eg, disperse or dissolve) a bifunctional surface modifier in a liquid carrier and use a concave plate The coating device transfers the liquid carrier to the polymer sheet. The carrier can then be removed from the surface of the polymer sheet by, for example, evaporation. The adhesion value of the obtained pvB sheet having a bifunctional surface modifier on the surface is at least about 50% lower than the adhesion value of the pvB resin polymer sheet containing no bifunctional surface modifier, preferably at least about 7〇%, and more preferably at least about 9〇/. . The transparency of a pVB sheet having a bifunctional surface modifier applied thereto can be determined by a haze value which is a transmission of light which is deflected from the direction of the incident beam by more than a specific angle due to scattering. The percentage can be determined in accordance with ASTM D1003. Preferably, the haze value is less than about 3%, more preferably less than about 2% ' and most preferably less than about. The presence of the bifunctional surface modifier has essentially no effect on the adhesion of the surface of the sheet containing the bifunctional surface modifier. Preferably, the difference between the puncture value (quantitative value of the degree of attachment of the PVB flakes to the glass) and the adhesion value of the PVB flakes having a dual-energy surface modifier on a surface not 93796.doc 1342320 The value is within about 20%, more preferably within about 1%, and most preferably within about 5%. Adhesion can be measured by, for example, a hit adhesion test that measures the bond between the PVB sheet and the glass. EXAMPLES The following tests were used in these examples: 1. Blast Adhesion Test A double glazing laminate sample was prepared under standard autoclave lamination conditions. The laminates were cooled to -1 7.8 t and manually broken with a hammer to break the glass. Then remove all the cullet that has not adhered to the PVB sheet, and the remaining amount of glass adhered to the PVB sheet corresponds to a set of standard implementation metrics, which corresponds to a scale scale, indicating that the point is attached to Different amounts of glass on the pvb sheet. Specifically, a hit criterion of zero means that no remaining glass adheres to the PVB sheet. A hit rating of 1 〇 indicates that 1% of the glass remains attached to the PVB sheet. 2. Adhesion test This test measures the self-adhesion tendency of PVB sheets. In this test, the two rectangular membranes were cut and placed together in pairs in complete overlap. The upper sheets of each pair are adhered to a strip of corresponding size. Place the pair of membranes in the center of the two steel plates and at 7. (The temperature was applied to the assembly at a temperature of 24 hours. The strip was peeled off at a speed of 84 inches per minute using a peel tester in a 90 degree peel test. The adhesion force was pounded per line. (pLi) to indicate. 3. % haze (transparency) test 93796.doc • 14-1342320 This test is used to measure the transparency of laminates made from PVB sheets in accordance with ASTM D1003-6 1 (1 977) In the year of re-examination, the A program was implemented, using the C light source 'observation angle of 2 degrees, the device for measuring the haze value used the D25 type haze meter purchased from Hunterlab. Example 1: PVB sheet manufacturing using a high intensity blend The plasticized PVB formulation used to make the PVB flakes was premixed, and the formulation contained 1 part by weight of pvB resin (16.3 wt% in terms of PVOH) and 52 parts of triethylene glycol II ( 2-ethyl hexanoate) and other additives (including adhesion control agents, UV absorbers, antioxidants, and other ingredients). The plasticized formulation is melted in an extruder and passed through a sheet in the form of a melt. Stamper (the front end of the stamper has a rectangular die, borrowed a pair of opposing lip boundaries. The temperature of the melt is about i 8 〇 < t. The thickness of the extruded sheet is about 3 mils (0 76 mm). Each side of the sheet has a thick I surface. Air can be removed from the interface between the sheet and the glass during the lamination process. 2 Example 2: Dip coating of P VB sheet The control sample can be subjected to a dip coating temperature to perform an energy surface of the control sample and such a mist. Degree test PVB 4 piece of impregnation coating was carried out by: PVB 4 sheets at room temperature were respectively impregnated with a corresponding bifunctional surface aqueous solution-stage Pb, for example, 2 sec, and then dried = Some samples will be immersed in the human - fresh water pool. - Some samples will be immersed in the high-coating "immersion coated sample and the humidity is adjusted to 3. 35%. Examples of impregnation conditions, including The type of double official modifier (surface modifier), solution concentration, impregnation time, and the hit test of 1 turn impregnation sample, adhesion test and the results of 93796.doc 1342320 are listed in Table 1, respectively. _4 A. Aqueous solution with sodium polystyrene sulfonate (pSSNa), DSH or DSNa The Tuwei sample was then subjected to a second impregnation in the water equal to the recorded impregnation time. Then the impact test, adhesion test and haze test were carried out. The test results are shown in Table 1 below: Table 1 Sample No. Surface Modification Sex Agent Control > Agronomic Immersion Time Adhesion Value (wt·%) (seconds) (PLI) ~ - 2.00 Haze % 0.50 Scratch Adhesion Test 6.6 2. 3. 4. 5. Control PSSNa3 2.0 60l DSH 2.0 601 DSNa 2.0 601 DSH 2.0 60' DSH 2.0 40' DSH 2.0 20' DSH 2.0 201,: DSH 1.0 20丨DSH 0.5 201 1.86 0.06 0.75 2.96 6.6 6.5 3.2 6.8 4.8 6.5 9.0 9.0 9.0 7.3 0.45 0.40 0.50 0.40 0.30 0.30 0.30 0.30 0.30 0.30 The duration of the solution and the recorded impregnation increased the temperature of the solution to 40. (: 3PSSNa represents the sodium salt of polystyrene sulfonic acid. After coating the coated sample with DSH aqueous solution of different concentration at different room temperature, it is subjected to impact test, adhesion test and fog. The test results are shown in Table 2 below: 93796.doc -16- 1342320 Table 2 Sample No. Surface Modifier Concentration (wt. %) Immersion Time (seconds) Adhesion Value (PLI) Haze % Hit Adhesion Sex test 12. - - - 4.14 0.40 7.5 Control 13. DSH 2.0 60 0.10 0.30 9.0 14. DSH 2.0 20 0.12 0.40 9.0 15. DSH 1.0 60 0.15 0.40 9.0 16. DSH 1.0 20 0.24 0.40 9.0 17. DSH 0.5 60 0.40 0.30 9.0 18. DSH 0.5 20 0.51 0.40 8.8 After immersing the coated sample with an aqueous solution of 1 wt.% DSH/DSNa mixture (which has various DSH/DSNa weight ratios) at different chambering times at room temperature, The impact test, adhesion test and haze test were carried out. The test results are shown in Table 3 below: Table 3 Sample No. Surface Modifier Concentration Immersion Time Adhesion Value Haze % Hit Adhesion (wt. %) ( Second) (PLI) Sex Test 19. - - - 2.80 0.50 6.2 Control 20. 100% DSH / 0% DSN a 1.0 60 0.03 0.40 9 21. 100% DSH/ 0% DSNa 1.0 20 0.04 0.40 9 22. 75% DSH/ 25% DSNa 1.0 60 0.04 0.40 9 23. 75% DSH/ 25% DSNa 1.0 20 0.07 0.60 9 24. 50% DSH/ 50% DSNa 1.0 60 0.05 0.40 4.5 25. 50% DSH/ 50% DSNa 1.0 20 0.06 0.50 6.5 DSH/DSNa (or DSMg) mixture at 1 wt.°/〇 at room temperature Different DSH/DSNa (or DSMg) weight ratio aqueous solutions were used to impregnate the 93796.doc 1342320 cloth sample for 20 seconds, and then subjected to a hit test, adhesion test and haze test. The test results are shown in Table 4 below. Show: Table 4 Sample No. Surface Modifier Concentration (wt.%) Immersion Time (seconds) Adhesion Value (PLI) Haze % Impact Adhesion Test 26. - - 3.50 0.6 6 Control 27. 100% DSH/ 0% DSNa 1 20 0.05 0.5 9 28. 75% DSH / 25% DSNa 1 20 0.05 0.5 9 29. 50% DSH / 50% DSNa 1 20 0.08 0.5 7.8 30. 25% DSH / 75% DSNa 1 20 0.07 0.5 3 31. 5% DSH/ 95% DSNa 1 20 0.08 0.5 0 32. 0%DSH/ 100% DSNa 1 20 0.09 0.5 0 33. 75% DSH/ 25% DSMg 1 20 0.07 0.5 9 34. 50% DSH / 50% DSMg 1 20 0.05 0.5 9 35. 25% DSH / 75% DSMg 1 20 0.10 0.5 8 36. 5% DSH / 95% DSMg 1 20 0.28 0.5 0 37. 0% DSH/ 100% DSMg 1 20 0.23 0.5 0 38. - - - 2.06 0.4 6.5 Control 39. 20% DSH/ 80% DSMg 1 20 0.02 0.3 1.5 40. 40% DSH/ 60% DSNa 1 20 0.04 0.4 8 41. 30%D SH/ 70% DSNa 1 20 0.04 0.3 7.5 93796.doc · 18· 1342320 42. 43. 20% DSH/ 80% DSNa 10% DSH/90% DSNa 20 20 0.07 0.22 0.3 0.3 6.5 5.5 The "β-sheet" embodiment with a bifunctional surface modifier applied above is generally suitable as a PVB interlayer for a layer of safety glass. In addition, the above-described embodiments, particularly 14 8 m U, are particularly suitable for use in the manufacture of non-alternating interposed acoustic PVB interlayer products because of the improved surface of the sheets. The above PVB sheets also have several other advantages over shaving sheets having no bifunctional surface modifier applied to the surface. First, the #connectivity of the PVB flakes coated with a bifunctional surface modifier is significantly reduced, while maintaining sufficient optical quality and proper adhesion to the glass when incorporated into laminated safety glass. The reduction in the tendency to stick allows the pvB sheet to be stored or transported at a lower refrigerated or alternately inserted requirement. Second, because at least the fragments of the bifunctional surface modifier disclosed above are compatible with the crucible, no additional processing steps, such as cleaning the flakes to remove the powder, are required. Other advantages of the invention will be readily apparent to those skilled in the art. Although the present invention has been described with reference to the present invention, it should be understood by those skilled in the art that the invention may be modified in various ways and may be substituted for equivalents thereof without departing from the scope of the invention. . In addition, many modifications may be made to the teachings of the present invention without departing from the scope of the invention. Therefore, the present invention is not intended to be limited to the specific embodiments disclosed as the preferred embodiment of the invention. 93796.doc -19-